Catalyst compositions and use thereof

ABSTRACT

This invention relates to novel transition metal catalyst compounds comprising four oxygen atoms bonded to a transition metal where two of the oxygen groups are bond to the metal by dative bonds, catalyst systems comprising such and polymerization processes using such.

PRIORITY CLAIM

This application is a 371 National Phase application ofPCT/US2017/039645, filed Jun. 28, 2017 which claims priority to and thebenefit of U.S. Ser. No. 62/367,814, filed Jul. 28, 2016 which isincorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to novel transition metal catalyst compoundscomprising four oxygen atoms bonded to a transition metal where two ofthe oxygen groups are bond to the metal by dative bonds, catalystsystems comprising such and polymerization processes using such.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hencethere is interest in finding new catalyst systems that increase thecommercial usefulness of the catalyst and allow the production ofpolymers having improved properties.

Journal of the American Chemical Society, 1995, 117, pp. 3008-3021discloses bis-phenoxides without dative bonds.

Journal of the American Chemical Society, 2005, 127(44), pp. 15528-15535discloses compounds with no dative bonds.

WO 2003/091262 and U.S. Pat. No. 7,060,848 disclose bridged biaromaticcatalyst complexes typically bridged via two heteroatoms.

Other references of interest include: U.S. Pat. No. 8,420,847; WO2012/027448; U.S. Pat. Nos. 9,029,487; 5,889,134; 6,020,452; US2013/0144018; US2004/0005984; US 2004/0010103; US 2004/0014950; U.S.Pat. Nos. 6,841,502; 6,869,904; US 2005/0080281; U.S. Pat. No.6,897,276; US 2005/0164872; U.S. Pat. No. 7,030,256; US 2006/0211892;U.S. Pat. Nos. 7,126,031; 7,241,715; US 2008/0269470; U.S. Pat. No.7,659,415; US 2006/0025548; US 2006/0052554; U.S. Pat. No. 7,091,292; US2006/0205588; U.S. Pat. No. 7,241,714; Inorganic Chemistry, 2000,39(16), pp. 3696-3704; Tetrahedron Letters, 1998, 39(43), pp. 7917-7920;Journal of Organic Chemistry, 1999, 64(21), pp. 7940-7956; Journal ofthe American Chemical Society, 2000, 122(10), pp. 2252-2260; Journal ofOrganic Chemistry, 1999, 64(12), pp. 4222-4223; Journal of OrganicChemistry, 2010, 75(20), pp. 6941-6952; Journal of Physical Chemistry,1993, 97(25), pp. 6590-6591, Brook, Acc. Chem. Res. 1974, 7, p. 77;Ghose, B. Journal of Organic Chemistry, 1979, 164(1), pp. 11-18;Organometallics, 1997, 16(20), pp. 4240-4242; Journal of MacromolecularScience, Part A, Pure and Applied Chemistry, 2007, 44, pp. 977-987;Journal of Organic Chemistry, 1999, 64, pp. 4222-4223; and Journal ofthe American Chemical Society, 2010, 132(16), pp. 5566-5567.

There is still a need in the art for new and improved catalyst systemsfor the polymerization of olefins, in order to achieve specific polymerproperties, such as high melting point, high molecular weights, toincrease conversion or comonomer incorporation, or to alter comonomerdistribution without deteriorating the resulting polymer's properties.

It is therefore an object of the present invention to novel catalystcompounds, catalysts systems comprising such compounds, and processesfor the polymerization of olefins using such compounds and systems.

SUMMARY OF THE INVENTION

This invention relates to a catalyst compound represented by theformula:

wherein:a dotted line indicates a dative bond;M is a group 4 metal;z is a number from 0 to 12, provided that when z is 0, then there is adirect bond between the phenyl rings in place of the (CH₂)_(z) group;each of R¹, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶is, independently, hydrogen, a substituted C₁ to C₄₀ hydrocarbyl group,a C₁ to C₄₀ unsubstituted hydrocarbyl group, or a heteroatom, providedthat any of adjacent R groups may form a fused ring or multicenter fusedring system where the rings may be aromatic, partially saturated orsaturated, and provided that R⁹ and R¹⁰ may not form a bridge;each of R² and R³, is, independently, hydrogen, a substituted C₁ to C₄₀hydrocarbyl group, a C₁ to C₄₀ unsubstituted hydrocarbyl group, or aheteroatom, provided that R² and R³ may not form a bridge; andeach X is, independently, a substituted C₁ to C₄₀ hydrocarbyl group, aC₁ to C₄₀ unsubstituted hydrocarbyl group, a hydride, an amide, analkoxide, a sulfide, a phosphide, a halide, an amine, a phosphines, anethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system).

This invention further relates to catalyst systems comprising the abovecatalyst compounds and an activator.

This invention also relates to a method to polymerize olefins comprisingcontacting the above catalyst compound with an activator and one or moremonomers, and preferably further comprising obtaining polymer.

DETAILED DESCRIPTION OF THE INVENTION

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as described inCHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985). Therefore, a “group4 metal” is an element from group 4 of the Periodic Table, e.g., Hf, Ti,Zr, or Rf.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, the olefin present in such polymer or copolymer is thepolymerized form of the olefin. For example, when a copolymer is said tohave an “ethylene” content of 35 wt % to 55 wt %, it is understood thata mer unit in the copolymer is derived from ethylene in thepolymerization reaction and said derived units are present at 35 wt % to55 wt %, based upon the weight of the copolymer. A “polymer” has two ormore of the same or different units. A “homopolymer” is a polymer havingmer units that are the same. A “copolymer” is a polymer having two ormore mer units that are different from each other. A “terpolymer” apolymer having three mer units that are different from each other.Accordingly, the definition of copolymer, as used herein, includesterpolymers and the like. “Different” as used to refer to mer unitsindicates that the mer units differ from each other by at least one atomor are different isomerically. An “ethylene polymer” or “ethylenecopolymer” is a polymer or copolymer comprising at least 50 mole %ethylene derived units, a “propylene polymer” or “propylene copolymer”is a polymer or copolymer comprising at least 50 mole % propylenederived units, a “butylene polymer” or “butylene copolymer” is a polymeror copolymer comprising at least 50 mole % butylene derived units, andso on.

For the purposes of this invention, ethylene shall be considered anα-olefin.

For purposes of this invention and claims thereto, unless otherwiseindicated, the term “substituted” means that a hydrogen or carbon atomhas been replaced with a heteroatom, or a heteroatom containing group.For example, a “substituted hydrocarbyl” is a radical made of carbon andhydrogen where at least one hydrogen or carbon atom is replaced by aheteroatom or heteroatom containing group, e.g., ethyl alcohol is anethyl group substituted with an —OH group. Useful substitutedhydrocarbyl radicals include radicals in which at least one hydrogenatom of the hydrocarbyl radical has been substituted with at least onehalogen (such as Br, Cl, F or I) or at least one functional group suchas NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃,SnR*₃, PbR*₃, and the like, or where at least one heteroatom has beeninserted within a hydrocarbyl ring.

As used herein, Mn is number average molecular weight, Mw is weightaverage molecular weight, and Mz is z average molecular weight, wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD), also referred to as polydispersity index or polydispersity (PDI),is defined to be Mw divided by Mn. Unless otherwise noted, all molecularweight units (e.g., Mw, Mn, Mz) are g/mol. The following abbreviationsmay be used herein: Me is methyl, Et is ethyl, Pr is propyl, cPR iscyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu isnormal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Octis octyl, MAO is methylalumoxane, dme is 1,2-dimethoxyethane, TMS istrimethylsilyl, TIBAL is triisobutylaluminum, TNOAL istri(n-octyl)aluminum, p-Me is para-methyl, Ph is phenyl, Bn or Bz isbenzyl (i.e., CH₂Ph), THF (also referred to as thf) is tetrahydrofuran,tol is toluene, EtOAc is ethyl acetate, and Cy is cyclohexyl.

A “catalyst system” is a combination of at least one catalyst compound,at least one activator, optional co-activator, and optional supportmaterial. For the purposes of this invention and the claims thereto,when catalyst systems are described as comprising neutral stable formsof the components, it is well understood by one of ordinary skill in theart, that the ionic form of the component is the form that reacts withthe monomers to produce polymers.

In the description herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, catalyst, catalyst compound, atransition metal compound, a transition metal complex, or a complex andthese terms are used interchangeably. Activator and cocatalyst are alsoused interchangeably. An “anionic ligand” is a negatively charged ligandwhich donates one or more pairs of electrons to a metal ion. A “neutraldonor ligand” is a neutrally charged ligand which donates one or morepairs of electrons to a metal ion.

For purposes of this invention and claims thereto in relation totransition metal catalyst compounds, the term “substituted” means that ahydrogen or carbon atom has been replaced with a hydrocarbyl group, aheteroatom, or a heteroatom containing group. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group.

The terms “hydrocarbyl radical,” “hydrocarbyl,” “hydrocarbyl group,”“alkyl radical,” and “alkyl” are used interchangeably throughout thisdocument. Likewise, the terms “group,” “radical,” and “substituent” arealso used interchangeably in this document. For purposes of thisdisclosure, “hydrocarbyl radical” is defined to be C₁-C₁₀₀ radicals,that may be linear, branched, or cyclic, and when cyclic, aromatic ornon-aromatic. Examples of such radicals include, but are not limited to,methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cyclooctyl, and the like including theirsubstituted analogues.

The term “alkenyl” means a straight-chain, branched-chain, or cyclichydrocarbon radical having one or more double bonds. These alkenylradicals may be optionally substituted. Examples of suitable alkenylradicals include, but are not limited to, ethenyl, propenyl, allyl,1,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl,cycloctenyl and the like including their substituted analogues.

The term “aryl” or “aryl group” means a six carbon aromatic ring and thesubstituted variants thereof, including but not limited to, phenyl,2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means anaryl group where a ring carbon atom (or two or thee ring carbon atoms)has been replaced with a heteroatom, preferably N, O, or S. As usedherein, the term “aromatic” also refers to pseudoaromatic heterocycleswhich are heterocyclic substituents that have similar properties andstructures (nearly planar) to aromatic heterocyclic ligands, but are notby definition aromatic; likewise the term aromatic also refers tosubstituted aromatics.

A scavenger is a compound that is typically added to facilitatepolymerization by scavenging impurities. Some scavengers may also act asactivators and may be referred to as co-activators. A co-activator, thatis not a scavenger, may also be used in conjunction with an activator inorder to form an active catalyst. In some embodiments, a co-activatorcan be pre-mixed with the transition metal compound to form an alkylatedtransition metal compound.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn.

A solution polymerization means a polymerization process in which thepolymer is dissolved in a liquid polymerization medium, such as an inertsolvent or monomer(s) or their blends.

A bulk polymerization means a polymerization process in which themonomers and/or comonomers being polymerized are used as a solvent ordiluent using little or no non-monomer inert solvent as a solvent ordiluent. A small fraction of inert solvent might be used as a carrierfor catalyst and scavenger. A bulk polymerization system contains lessthan 25 wt % of inert solvent or diluent, preferably less than 10 wt %,preferably less than 1 wt %, preferably 0 wt %.

Catalyst Compounds

The transition metal compounds described herein are typically moleculesin which an ancillary ligand is coordinated to a central transitionmetal atom. The ligand is bulky and stably bonded to the transitionmetal so as to maintain its influence during use of the catalyst, suchas polymerization. The ligand may be coordinated to the transition metalby covalent bond and/or electron donation coordination or intermediatebonds. The transition metal compounds are generally subjected toactivation to perform their polymerization or oligomerization functionusing an activator which is believed to create a cation as a result ofthe removal of an anionic group, often referred to as a leaving group,from the transition metal.

In a preferred embodiment, this invention related to a catalystcompound, and catalyst systems comprising such compounds, represented bythe formula:

wherein: a dotted line indicates a dative bond;M is a group 4 metal, such as Hf, Zr, or Ti, preferably Ti;z is a number from 0 to 12, e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,or 12, preferably 0, 1, 2, 3, 4 or 5, provided that when z is 0, thenthere is a direct bond between the phenyl rings in place of the(CH₂)_(z) group in the formula above (as shown below);each of R¹, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶is, independently, hydrogen, a substituted C₁ to C₄₀ hydrocarbyl group,a C₁ to C₄₀ unsubstituted hydrocarbyl group, or a heteroatom, providedthat any of adjacent R groups may form a fused ring or multicenter fusedring system where the rings may be aromatic, partially saturated orsaturated, and provided that R⁹ and R¹⁰ may not form a bridge;each of R² and R³, is, independently, hydrogen, a substituted C₁ to C₄₀hydrocarbyl group, a C₁ to C₄₀ unsubstituted hydrocarbyl group, or aheteroatom, provided that R² and R³ may not form a bridge; andeach X is, independently, a substituted C₁ to C₄₀ hydrocarbyl group, aC₁ to C₄₀ unsubstituted hydrocarbyl group, a hydride, an amide, analkoxide, a sulfide, a phosphide, a halide, an amine, a phosphines, anethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system), preferably each X is independently selected fromhalides (Cl, Br, F, I,) and C₁ to C₅ alkyl groups (e.g., methyl, ethyl,propyl, butyl, pentyl or an isomer thereof), preferably each X is adimethylamido, benzyl or methyl group.

In a preferred embodiment of the invention, each R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ is, independently, is,independently, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, docecyl, t-butyl, isopropyl,phenyl, napthyl, or an isomer thereof.

In a preferred embodiment of the invention, each R² and R³ is,independently, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, docecyl, t-butyl, isopropyl, phenyl,napthyl, or an isomer thereof.

This invention also relates to embodiments where z is zero, e.g.,

where the dotted line, M, X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are as described above.

In any embodiment described herein, M is Ti and R is t-butyl.

For purposes of this invention and the claims thereto, the followingnumbering scheme is used:

Thus the following would be named as:

1,2-[(3-biphenyl)(2′-methoxy-3-biphenyl)]ethane

Catalyst compounds that are particularly useful in this inventioninclude 1,2-bis(2′methoxy,2-oxy,3-biphenyl)ethane titaniumbis(dimethylamine).

Particularly useful catalyst compounds include those represented by theformula:

wherein Me is methyl, Et is ethyl, Bz is benzyl, Ph is phenyl, tBu ist-butyl, and the dotted line indicates a dative bond.

In a preferred embodiment in any of the processes described herein, onecatalyst compound is used, e.g., the catalyst compounds are notdifferent. For purposes of this invention one catalyst compound isconsidered different from another if they differ by at least one atom.For example, “1,2-bis(2′ethoxy,2-oxy,3-biphenyl)ethane titaniumbis(dimethylamine)” is different from“1,2-bis(2′methoxy,2-oxy,3-biphenyl)ethane titanium bis(dimethylamine).”Catalyst compounds that differ only by isomer are considered the samefor purposes if this invention.

In some embodiments, two or more different catalyst compounds arepresent in the catalyst system used herein. In some embodiments, two ormore different catalyst compounds are present in the reaction zone wherethe process(es) described herein occur. When two transition metalcompound based catalysts are used in one reactor as a mixed catalystsystem, the two transition metal compounds are preferably chosen suchthat the two are compatible. A simple screening method such as by ¹H or¹³C NMR, known to those of ordinary skill in the art, can be used todetermine which transition metal compounds are compatible. It ispreferable to use the same activator for the transition metal compounds,however, two different activators, such as a non-coordinating anionactivator and an alumoxane, can be used in combination. If one or moretransition metal compounds contain an X ligand which is not a hydride,hydrocarbyl, or substituted hydrocarbyl, then the alumoxane may becontacted with the transition metal compounds prior to addition of thenon-coordinating anion activator.

The two transition metal compounds (pre-catalysts) may be used in anyratio. Preferred molar ratios of (A) transition metal compound to (B)transition metal compound fall within the range of (A:B) 1:1000 to1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1,alternatively 1:1 to 100:1, alternatively 1:1 to 75:1, and alternatively5:1 to 50:1. The particular ratio chosen will depend on the exactpre-catalysts chosen, the method of activation, and the end productdesired. In a particular embodiment, when using the two pre-catalysts,where both are activated with the same activator, useful mole percents,based upon the molecular weight of the pre-catalysts, are 10 to 99.9% Ato 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50% B,alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99% Ato 1 to 10% B.

Methods to Prepare the Catalyst Compounds.

Catalyst compounds described herein can be prepared by the generalpathway shown below:

where M and X are as defined above, R is as defined for R⁴ above, R′ isas defined for R² above, x is a number from 0 to 12, e.g., 0, 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, or 12, and THP is tetrahydropyran.Activators

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.

After the complexes described above have been synthesized, catalystsystems may be formed by combining them with activators in any mannerknown from the literature including by supporting them for use in slurryor gas phase polymerization. The catalyst systems may also be added toor generated in solution polymerization or bulk polymerization (in themonomer). The catalyst system typically comprises a complex as describedabove and an activator such as alumoxane or a non-coordinating anion.

Non-limiting activators, for example, include alumoxanes, aluminumalkyls, ionizing activators, which may be neutral or ionic, andconventional-type cocatalysts. Preferred activators typically includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

Alumoxane Activators

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst system. Alumoxanes are generally oligomeric compoundscontaining —Al(R*)—O— sub-units, where R* is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the abstractable ligand is an alkyl, halide, alkoxideor amide. Mixtures of different alumoxanes and modified alumoxanes mayalso be used. It may be preferable to use a visually clearmethylalumoxane. A cloudy or gelled alumoxane can be filtered to producea clear solution or clear alumoxane can be decanted from the cloudysolution. A useful alumoxane is a modified methyl alumoxane (MMAO)cocatalyst type 3A (commercially available from Akzo Chemicals, Inc.under the trade name Modified Methylalumoxane type 3A, covered underU.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), someembodiments select the maximum amount of activator typically at up to a5000-fold molar excess Al/M over the catalyst compound (per metalcatalytic site). The minimum activator-to-catalyst-compound is a 1:1molar ratio. Alternate preferred ranges include from 1:1 to 500:1,alternately from 1:1 to 200:1, alternately from 1:1 to 100:1, oralternately from 1:1 to 50:1.

In an alternate embodiment, little or no alumoxane is used in thepolymerization processes described herein. Preferably, alumoxane ispresent at zero mole %; alternately the alumoxane is present at a molarratio of aluminum to catalyst compound transition metal less than 500:1,preferably less than 300:1, preferably less than 100:1, preferably lessthan 1:1.

Non-Coordinating Anion Activators

A non-coordinating anion (NCA) is defined to mean an anion either thatdoes not coordinate to the catalyst metal cation or that does coordinateto the metal cation, but only weakly. The term NCA is also defined toinclude multicomponent NCA-containing activators, such asN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain anacidic cationic group and the non-coordinating anion. The term NCA isalso defined to include neutral Lewis acids, such astris(pentafluorophenyl)boron, that can react with a catalyst to form anactivated species by abstraction of an anionic group. An NCA weaklyenough that a neutral Lewis base, such as an olefinically oracetylenically unsaturated monomer can displace it from the catalystcenter. Any metal or metalloid that can form a compatible, weaklycoordinating complex may be used or contained in the non-coordinatinganion. Suitable metals include, but are not limited to, aluminum, gold,and platinum. Suitable metalloids include, but are not limited to,boron, aluminum, phosphorus, and silicon. A stoichiometric activator canbe either neutral or ionic. The terms ionic activator, andstoichiometric ionic activator can be used interchangeably. Likewise,the terms neutral stoichiometric activator, and Lewis acid activator canbe used interchangeably. The term non-coordinating anion includesneutral stoichiometric activators, ionic stoichiometric activators,ionic activators, and Lewis acid activators.

“Compatible” non-coordinating anions are those which are not degraded toneutrality when the initially formed complex decomposes. Further, theanion will not transfer an anionic substituent or fragment to the cationso as to cause it to form a neutral transition metal compound and aneutral by-product from the anion. Non-coordinating anions useful inaccordance with this invention are those that are compatible, stabilizethe transition metal cation in the sense of balancing its ionic chargeat +1, and yet retain sufficient lability to permit displacement duringpolymerization.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenylboron metalloid precursor or a tris perfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459), or combination thereof. It is also within thescope of this invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

The catalyst systems of this invention can include at least onenon-coordinating anion (NCA) activator.

In preferred embodiment, boron containing NCA activators represented bythe formula below can be used:Z_(d) ⁺(A^(d−))where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base;H is hydrogen; (L-H) is a Bronsted acid; A^(d−) is a boron containingnon-coordinating anion having the charge d−; d is 1, 2, or 3.

The cation component, Z_(d) ⁺ may include Bronsted acids such as protonsor protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from thetransition metal catalyst precursor, resulting in a cationic transitionmetal species.

The activating cation Z_(d) ⁺ may also be a moiety such as silver,tropylium, carboniums, ferroceniums and mixtures, preferably carboniumsand ferroceniums. Most preferably Z_(d) ⁺ is triphenyl carbonium.Preferred reducible Lewis acids can be any triaryl carbonium (where thearyl can be substituted or unsubstituted, such as those represented bythe formula: (Ar₃C⁺), where Ar is aryl or aryl substituted with aheteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀hydrocarbyl), preferably the reducible Lewis acids in formula (14) aboveas “Z” include those represented by the formula: (Ph₃C), where Ph is asubstituted or unsubstituted phenyl, preferably substituted with C₁ toC₄₀ hydrocarbyls or substituted a C₁ to C₄₀ hydrocarbyls, preferably C₁to C₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics,preferably Z is a triphenylcarbonium.

When Z_(d) ⁺ is the activating cation (L-H)_(d) ⁺, it is preferably aBronsted acid, capable of donating a proton to the transition metalcatalytic precursor resulting in a transition metal cation, includingammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof,preferably ammoniums of methylamine, aniline, dimethylamine,diethylamine, N-methylaniline, diphenylamine, trimethylamine,triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine,p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniumsfrom triethylphosphine, triphenylphosphine, and diphenylphosphine,oxomiuns from ethers such as dimethyl ether diethyl ether,tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethylthioethers, tetrahydrothiophene, and mixtures thereof.

The anion component A^(d−) includes those having the formula[M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6(preferably 1, 2, 3, or 4); n−k=d; M is an element selected from Group13 of the Periodic Table of the Elements, preferably boron or aluminum,and Q is independently a hydride, bridged or unbridged dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbylradicals, said Q having up to 20 carbon atoms with the proviso that innot more than 1 occurrence is Q a halide. Preferably, each Q is afluorinated hydrocarbyl group having 1 to 20 carbon atoms, morepreferably each Q is a fluorinated aryl group, and most preferably eachQ is a pentafluoryl aryl group. Examples of suitable A^(d−) also includediboron compounds as disclosed in U.S. Pat. No. 5,447,895, which isfully incorporated herein by reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst are the compounds described as (andparticularly those specifically listed as) activators in U.S. Pat. No.8,658,556, which is incorporated by reference herein.

Most preferably, the ionic stoichiometric activator Z_(d) ⁺(A^(d−)) isone or more of N,N-dimethylanilinium tetra(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate.

Bulky activators are also useful herein as NCAs. “Bulky activator” asused herein refers to anionic activators represented by the formula:

where:each R₁ is, independently, a halide, preferably a fluoride;Ar is substituted or unsubstituted aryl group (preferably a substitutedor unsubstituted phenyl), preferably substituted with C₁ to C₄₀hydrocarbyls, preferably C₁ to C₂₀ alkyls or aromatics;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferablyR₂ is a fluoride or a perfluorinated phenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl group); wherein R₂ and R₃ canform one or more saturated or unsaturated, substituted or unsubstitutedrings (preferably R₂ and R₃ form a perfluorinated phenyl ring); andL is a neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3;wherein the anion has a molecular weight of greater than 1020 g/mol;wherein at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.

Preferably (Ar₃C)_(d) ⁺ is (Ph₃C)_(d) ⁺, where Ph is a substituted orunsubstituted phenyl, preferably substituted with C₁ to C₄₀ hydrocarbylsor substituted C₁ to C₄₀ hydrocarbyls, preferably C₁ to C₂₀ alkyls oraromatics or substituted C₁ to C₂₀ alkyls or aromatics.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple “Back of theEnvelope” Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3V_(s), where V_(s) is the scaledvolume. V_(s) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(s) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

For a list of particularly useful Bulky activators please see U.S. Pat.No. 8,658,556, which is incorporated by reference herein.

In another embodiment, one or more of the NCA activators is chosen fromthe activators described in U.S. Pat. No. 6,211,105.

Preferred activators include N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph₃C+][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄⁻],1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triaryl carbonium(such as triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator comprises one or more oftrialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl)borate, trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl,propyl, n-butyl, sec-butyl, or t-butyl).

The typical activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is about a 1:1 molar ratio. Alternatepreferred ranges include from 0.1:1 to 100:1, alternately from 0.5:1 to200:1, alternately from 1:1 to 500:1, alternately from 1:1 to 1000:1. Aparticularly useful range is from 0.5:1 to 10:1, preferably 1:1 to 5:1.

It is also within the scope of this invention that the catalystcompounds can be combined with combinations of alumoxanes and NCA's (seefor example, U.S. Pat. Nos. 5,153,157; 5,453,410; EP 0 573 120 BI; WO94/07928; and WO 95/14044 which discuss the use of an alumoxane incombination with an ionizing activator).

Chain Transfer Agents

Useful chain transfer agents are typically alkylalumoxanes, a compoundrepresented by the formula AlR₃, ZnR₂ (where each R is, independently, aC₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl, butyl, penyl,hexyl octyl or an isomer thereof) or a combination thereof, such asdiethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum,trioctylaluminum, or a combination thereof.

Optional Scavengers or Co-Activators

In addition to these activator compounds, scavengers or co-activatorsmay be used. Aluminum alkyl or organoaluminum compounds which may beutilized as scavengers or co-activators include, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.

Optional Support Materials

In embodiments herein, the catalyst system may comprise an inert supportmaterial. Preferably the supported material is a porous supportmaterial, for example, talc, and inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other organic orinorganic support material and the like, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finelydivided form. Suitable inorganic oxide materials for use in catalystsystems herein include Groups 2, 4, 13, and 14 metal oxides, such assilica, alumina, and mixtures thereof. Other inorganic oxides that maybe employed either alone or in combination with the silica, or aluminaare magnesia, titania, zirconia, and the like. Other suitable supportmaterials, however, can be employed, for example, finely dividedfunctionalized polyolefins, such as finely divided polyethylene.Particularly useful supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania, and the like. Preferredsupport materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof,more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 m. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 m. Mostpreferably, the surface area of the support material is in the range offrom about 100 to about 400 m²/g, pore volume from about 0.8 to about3.0 cc/g and average particle size is from about 5 to about 100 m. Theaverage pore size of the support material useful in the invention is inthe range of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 350 Å. In some embodiments, the support materialis a high surface area, amorphous silica (surface area=300 m²/gm; porevolume of 1.65 cm³/gm). Preferred silicas are marketed under the tradenames of DAVISON 952 or DAVISON 955 by the Davison Chemical Division ofW.R. Grace and Company. In other embodiments DAVISON 948 is used.

The support material should be dry, that is, free of absorbed water.Drying of the support material can be effected by heating or calciningat about 100° C. to about 1000° C., preferably at least about 600° C.When the support material is silica, it is heated to at least 200° C.,preferably about 200° C. to about 850° C., and most preferably at about600° C.; and for a time of about 1 minute to about 100 hours, from about12 hours to about 72 hours, or from about 24 hours to about 60 hours.The calcined support material must have at least some reactive hydroxyl(OH) groups to produce supported catalyst systems of this invention. Thecalcined support material is then contacted with at least onepolymerization catalyst comprising at least one catalyst compound and anactivator.

The support material, having reactive surface groups, typically hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a catalyst compound and an activator. Insome embodiments, the slurry of the support material is first contactedwith the activator for a period of time in the range of from about 0.5hours to about 24 hours, from about 2 hours to about 16 hours, or fromabout 4 hours to about 8 hours. The solution of the catalyst compound isthen contacted with the isolated support/activator. In some embodiments,the supported catalyst system is generated in situ. In alternateembodiment, the slurry of the support material is first contacted withthe catalyst compound for a period of time in the range of from about0.5 hours to about 24 hours, from about 2 hours to about 16 hours, orfrom about 4 hours to about 8 hours. The slurry of the supportedcatalyst compound is then contacted with the activator solution.

The mixture of the catalyst, activator and support is heated to about 0°C. to about 70° C., preferably to about 23° C. to about 60° C.,preferably at room temperature. Contact times typically range from about0.5 hours to about 24 hours, from about 2 hours to about 16 hours, orfrom about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator, and the catalyst compound, are atleast partially soluble and which are liquid at reaction temperatures.Preferred non-polar solvents are alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, may also be employed.

Polymerization Processes

In embodiments herein, the invention relates to polymerization processeswhere monomer (such as propylene), and optionally comonomer, arecontacted with a catalyst system comprising an activator and at leastone catalyst compound, as described above. The catalyst compound andactivator may be combined in any order, and are combined typically priorto contacting with the monomer.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, preferably C₂ to C₂₀ alpha olefins, preferably C₂ to C₁₂alpha olefins, preferably ethylene, propylene, butene, pentene, hexene,heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.In a preferred embodiment of the invention, the monomer comprisespropylene and an optional comonomers comprising one or more ethylene orC₄ to C₄₀ olefins, preferably C₄ to C₂₀ olefins, or preferably C₆ to C₁₂olefins. The C₄ to C₄₀ olefin monomers may be linear, branched, orcyclic. The C₄ to C₄₀ cyclic olefins may be strained or unstrained,monocyclic or polycyclic, and may optionally include heteroatoms and/orone or more functional groups. In another preferred embodiment, themonomer comprises ethylene and an optional comonomers comprising one ormore C₃ to C₄₀ olefins, preferably C₄ to C₂₀ olefins, or preferably C₆to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may be linear, branched,or cyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained,monocyclic or polycyclic, and may optionally include heteroatoms and/orone or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, preferably hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives.

In a preferred embodiment, one or more dienes are present in the polymerproduced herein at up to 10 weight %, preferably at 0.00001 to 1.0weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003to 0.2 weight %, based upon the total weight of the composition. In someembodiments, 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments, at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C4 to C30, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.,di-vinyl monomers). More preferably, the diolefin monomers are lineardi-vinyl monomers, most preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbomadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

Polymerization processes of this invention can be carried out in anymanner known in the art. Any suspension, homogeneous, bulk, solution,slurry, or gas phase polymerization process known in the art can beused. Such processes can be run in a batch, semi-batch, or continuousmode. Homogeneous polymerization processes and slurry processes arepreferred. (A homogeneous polymerization process is defined to be aprocess where at least 90 wt % of the product is soluble in the reactionmedia. A solution process is typically a homogeneous process.) A bulkhomogeneous process is particularly preferred. (A bulk process ispreferably a process where monomer concentration in all feeds to thereactor is 70 volume % or more.) Alternately, no solvent or diluent ispresent or added in the reaction medium, (except for the small amountsused as the carrier for the catalyst system or other additives, oramounts typically found with the monomer; e.g., propane in propylene).In another embodiment, the process is a slurry process. As used hereinthe term “slurry polymerization process” means a polymerization processwhere a supported catalyst is employed and monomers are polymerized onthe supported catalyst particles. At least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, 1-decene, and mixtures thereof. In a preferred embodiment,aliphatic hydrocarbon solvents are used as the solvent, such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In another embodiment, thesolvent is not aromatic; preferably aromatics are present in the solventat less than 1 wt %, preferably less than 0.5 wt %, preferably less than0 wt % based upon the weight of the solvents.

In a preferred embodiment, the feed concentration of the monomers andcomonomers for the polymerization is 60 vol % solvent or less,preferably 40 vol % or less, or preferably 20 vol % or less, based onthe total volume of the feedstream. Preferably the polymerization is runin a bulk process.

Preferred polymerizations can be run at any temperature and/or pressuresuitable to obtain the desired ethylene polymers. Typical temperaturesand/or pressures include a temperature in the range of from about 0° C.to about 300° C., preferably about 20° C. to about 200° C., preferablyabout 35° C. to about 150° C., preferably from about 40° C. to about120° C., preferably from about 45° C. to about 80° C.; and at a pressurein the range of from about 0.35 MPa to about 10 MPa, preferably fromabout 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about4 MPa.

In a typical polymerization, the run time of the reaction is up to 300minutes, preferably in the range of from about 5 to 250 minutes, orpreferably from about 10 to 120 minutes.

In some embodiments, hydrogen is present in the polymerization reactorat a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferablyfrom 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig(0.7 to 70 kPa).

In a preferred embodiment, little or no alumoxane is used in the processto produce the polymers. Preferably, alumoxane is present at zero mol %;alternately the alumoxane is present at a molar ratio of aluminum totransition metal less than 500:1, preferably less than 300:1, preferablyless than 100:1, preferably less than 1:1.

In a preferred embodiment, little or no scavenger is used in the processto produce the ethylene polymer. Preferably, scavenger (such as trialkyl aluminum) is present at zero mol %, alternately the scavenger ispresent at a molar ratio of scavenger metal to transition metal of lessthan 100:1, preferably less than 50:1, preferably less than 15:1,preferably less than 10:1.

In a preferred embodiment, the polymerization: 1) is conducted attemperatures of 0 to 300° C. (preferably 25 to 150° C., preferably 40 to120° C., preferably 45 to 80° C.); 2) is conducted at a pressure ofatmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferablyfrom 0.45 to 6 MPa, preferably from 0.5 to 4 MPa); 3) is conducted in analiphatic hydrocarbon solvent (such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; preferably where aromatics are preferably present in thesolvent at less than 1 wt %, preferably less than 0.5 wt %, preferablyat 0 wt % based upon the weight of the solvents); 4) wherein thecatalyst system used in the polymerization comprises less than 0.5 mol%, preferably 0 mol % alumoxane, alternately the alumoxane is present ata molar ratio of aluminum to transition metal less than 500:1,preferably less than 300:1, preferably less than 100:1, preferably lessthan 1:1; 5) the polymerization preferably occurs in one reaction zone;6) the productivity of the catalyst compound is at least 80,000g/mmol/hr (preferably at least 150,000 g/mmol/hr, preferably at least200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably atleast 300,000 g/mmol/hr); 7) optionally scavengers (such as trialkylaluminum compounds) are absent (e.g. present at zero mol %, alternatelythe scavenger is present at a molar ratio of scavenger metal totransition metal of less than 100:1, preferably less than 50:1,preferably less than 15:1, preferably less than 10:1); and 8) optionallyhydrogen is present in the polymerization reactor at a partial pressureof 0.001 to 50 psig (0.007 to 345 kPa) (preferably from 0.01 to 25 psig(0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa)). In apreferred embodiment, the catalyst system used in the polymerizationcomprises no more than one catalyst compound. A “reaction zone” alsoreferred to as a “polymerization zone” is a vessel where polymerizationtakes place, for example a batch reactor. When multiple reactors areused in either series or parallel configuration, each reactor isconsidered as a separate polymerization zone. For a multi-stagepolymerization in both a batch reactor and a continuous reactor, eachpolymerization stage is considered as a separate polymerization zone. Ina preferred embodiment, the polymerization occurs in one reaction zone.

Other additives may also be used in the polymerization, as desired, suchas one or more scavengers, promoters, modifiers, chain transfer agents(useful chain transfer agents are described above), reducing agents,oxidizing agents, hydrogen, aluminum alkyls, or silanes.

Polyolefin Products

This invention also relates to compositions of matter produced by themethods described herein.

In a preferred embodiment, the process described herein producespropylene homopolymers or propylene copolymers, such aspropylene-ethylene and/or propylene-alphaolefin (preferably C3 to C20)copolymers (such as propylene-hexene copolymers or propylene-octenecopolymers) having: a Mw/Mn of greater than 1 to 4 (preferably greaterthan 1 to 3).

Likewise, the process of this invention produces olefin polymers,preferably polyethylene and polypropylene homopolymers and copolymers.In a preferred embodiment, the polymers produced herein are homopolymersof ethylene or propylene, are copolymers of ethylene preferably havingfrom 0 to 25 mole % (alternately from 0.5 to 20 mole %, alternately from1 to 15 mole %, preferably from 3 to 10 mole %) of one or more C₃ to C₂₀olefin comonomer (preferably C₃ to C₁₂ alpha-olefin, preferablypropylene, butene, hexene, octene, decene, dodecene, preferablypropylene, butene, hexene, octene), or are copolymers of propylenepreferably having from 0 to 25 mole % (alternately from 0.5 to 20 mole%, alternately from 1 to 15 mole %, preferably from 3 to 10 mole %) ofone or more of C₂ or C₄ to C₂₀ olefin comonomer (preferably ethylene orC₄ to C₁₂ alpha-olefin, preferably ethylene, butene, hexene, octene,decene, dodecene, preferably ethylene, butene, hexene, octene).

In a preferred embodiment, the monomer is ethylene and the comonomer ishexene, preferably from 1 to 15 mole % hexene, alternately 1 to 10 mole%.

Typically, the polymers produced herein have an Mw of 5,000 to 1,000,000g/mol (preferably 25,000 to 750,000 g/mol, preferably 50,000 to 500,000g/mol), and/or an Mw/Mn of greater than 1 to 40 (alternately 1.2 to 20,alternately 1.3 to 10, alternately 1.4 to 5, 1.5 to 4, alternately 1.5to 3).

In a preferred embodiment the polymer produced herein has a unimodal ormultimodal molecular weight distribution as determined by Gel PermeationChromotography (GPC). By “unimodal” is meant that the GPC trace has onepeak or inflection point. By “multimodal” is meant that the GPC tracehas at least two peaks or inflection points. An inflection point is thatpoint where the second derivative of the curve changes in sign (e.g.,from negative to positive or vice versus).

Unless otherwise indicated Mw, Mn, MWD are determined by GPC asdescribed in US 2006/0173123 pages 24-25, paragraphs [0334] to [0341].

In a preferred embodiment, the polymer produced herein has a compositiondistribution breadth index (CDBI) of 50% or more, preferably 60% ormore, preferably 70% or more. CDBI is a measure of the compositiondistribution of monomer within the polymer chains and is measured by theprocedure described in PCT publication WO 93/03093, published Feb. 18,1993, specifically columns 7 and 8 as well as in Wild et al, J. Poly.Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S. Pat. No.5,008,204, including that fractions having a weight average molecularweight (Mw) below 15,000 are ignored when determining CDBI.

Blends

In another embodiment, the polymer (preferably the polyethylene orpolypropylene) produced herein is combined with one or more additionalpolymers prior to being formed into a film, molded part or otherarticle. Other useful polymers include polyethylene, isotacticpolypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene, and/orbutene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE,HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers ofacrylic acid, polymethylmethacrylate or any other polymers polymerizableby a high-pressure free radical process, polyvinylchloride,polybutene-1, isotactic polybutene, ABS resins, ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic blockcopolymers, polyamides, polycarbonates, PET resins, cross linkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, polyacetal,polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

In a preferred embodiment, the polymer (preferably the polyethylene orpolypropylene) is present in the above blends, at from 10 to 99 wt %,based upon the weight of the polymers in the blend, preferably 20 to 95wt %, even more preferably at least 30 to 90 wt %, even more preferablyat least 40 to 90 wt %, even more preferably at least 50 to 90 wt %,even more preferably at least 60 to 90 wt %, even more preferably atleast 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of theinvention with one or more polymers (as described above), by connectingreactors together in series to make reactor blends or by using more thanone catalyst in the same reactor to produce multiple species of polymer.The polymers can be mixed together prior to being put into the extruderor may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such asIRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites(e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

Films

Specifically, any of the foregoing polymers, such as the foregoingpolypropylenes or blends thereof, may be used in a variety of end-useapplications. Such applications include, for example, mono- ormulti-layer blown, extruded, and/or shrink films. These films may beformed by any number of well known extrusion or coextrusion techniques,such as a blown bubble film processing technique, wherein thecomposition can be extruded in a molten state through an annular die andthen expanded to form a uni-axial or biaxial orientation melt prior tobeing cooled to form a tubular, blown film, which can then be axiallyslit and unfolded to form a flat film. Films may be subsequentlyunoriented, uniaxially oriented, or biaxially oriented to the same ordifferent extents. One or more of the layers of the film may be orientedin the transverse and/or longitudinal directions to the same ordifferent extents. The uniaxially orientation can be accomplished usingtypical cold drawing or hot drawing methods. Biaxial orientation can beaccomplished using tenter frame equipment or a double bubble processesand may occur before or after the individual layers are broughttogether. For example, a polyethylene layer can be extrusion coated orlaminated onto an oriented polypropylene layer or the polyethylene andpolypropylene can be coextruded together into a film then oriented.Likewise, oriented polypropylene could be laminated to orientedpolyethylene or oriented polyethylene could be coated onto polypropylenethen optionally the combination could be oriented even further.Typically the films are oriented in the Machine Direction (MD) at aratio of up to 15, preferably between 5 and 7, and in the TransverseDirection (TD) at a ratio of up to 15, preferably 7 to 9. However, inanother embodiment the film is oriented to the same extent in both theMD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 to 50 m are usually suitable. Filmsintended for packaging are usually from 10 to 50 m thick. The thicknessof the sealing layer is typically 0.2 to 50 μm. There may be a sealinglayer on both the inner and outer surfaces of the film or the sealinglayer may be present on only the inner or the outer surface.

In another embodiment, one or more layers may be modified by coronatreatment, electron beam irradiation, gamma irradiation, flametreatment, or microwave. In a preferred embodiment, one or both of thesurface layers is modified by corona treatment.

In another embodiment, this invention relates to:

1. A catalyst compound represented by the formula:

wherein:a dotted line indicates a dative bond;M is a group 4 metal;z is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, provided that when zis 0, then there is a direct bond between the phenyl rings in place ofthe (CH₂)z group;each of R¹, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶is, independently, hydrogen, a substituted C₁ to C₄₀ hydrocarbyl group,a C₁ to C₄₀ unsubstituted hydrocarbyl group, or a heteroatom, providedthat any of adjacent R groups may form a fused ring or multicenter fusedring system where the rings may be aromatic, partially saturated orsaturated, and provided that R⁹ and R¹⁰ may not form a bridge;each of R² and R³, is, independently, hydrogen, a substituted C₁ to C₄₀hydrocarbyl group, a C₁ to C₄₀ unsubstituted hydrocarbyl group, or aheteroatom, provided that R² and R³ may not form a bridge; andeach X is, independently, a substituted C₁ to C₄₀ hydrocarbyl group, aC₁ to C₄₀ unsubstituted hydrocarbyl group, a hydride, an amide, analkoxide, a sulfide, a phosphide, a halide, an amine, a phosphines, anethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system).2. The compound of paragraph 1, wherein each of R² and R³, is,independently, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, docecyl, t-butyl, isopropyl,phenyl, napthyl or an isomer thereof.3. The compound of paragraph 1 or 2, wherein each X is independentlyselected from C₁, Br, F, I, methyl, ethyl, propyl, butyl, pentyl, benzylor an isomer thereof, and dimethylamido; or each X is, independently,selected from the group consisting of hydrocarbyl radicals having from 1to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides,halides, dienes, amines, phosphines, ethers, and a combination thereof,(two X's may form a part of a fused ring or a ring system).4. The compound of paragraph 1, 2, or 3 wherein M is Ti and each of R¹,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ is,independently, hydrogen or t-butyl.5. The compound of any of paragraphs 1 to 3, wherein M is Hf, Ti and/orZr.6. The compound of any of paragraphs 1 to 5, z is 2, 3, 4, 5, 6, 7, 8,9, 10, 11, or 12.7. The compound of any of paragraphs 1 to 6, wherein the catalystcompound comprises one or more catalyst compounds represented by theformula:

wherein Me is methyl, Et is ethyl, Bz is benzyl, Ph is phenyl, tBu ist-butyl, and the dotted line indicates a dative bond.8. A catalyst system comprising activator, the catalyst compound of anyof paragraphs 1 to 7, and optional support.9. The catalyst system of paragraph 8, further comprising chain transferagent represented by the formula AlR₃, ZnR₂ (where each R is,independently, a C₁-C₈ aliphatic radical, preferably methyl, ethyl,propyl, butyl, penyl, hexyl, octyl, or an isomer thereof) or acombination thereof.10. The catalyst system of paragraph 8 or 9, wherein the activatorcomprises alumoxane and or a non coordinating anion.11. A process to polymerize olefins comprising contacting one or moreolefins with the catalyst system of any of paragraphs 8 to 10.12. The process of paragraph 11, wherein the activator is one or moreof:

-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis(pentafluorophenyl)borate,-   trimethylammonium tetrakis(perfluoronaphthyl)borate,-   triethylammonium tetrakis(perfluoronaphthyl)borate,-   tripropylammonium tetrakis(perfluoronaphthyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)    tetrakis(perfluoronaphthyl)borate,-   tropillium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylphosphonium tetrakis(perfluoronaphthyl)borate,-   triethylsilylium tetrakis(perfluoronaphthyl)borate,-   benzene(diazonium) tetrakis(perfluoronaphthyl)borate,-   trimethylammonium tetrakis(perfluorobiphenyl)borate,-   triethylammonium tetrakis(perfluorobiphenyl)borate,-   tripropylammonium tetrakis(perfluorobiphenyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   tri(t-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)    tetrakis(perfluorobiphenyl)borate,-   tropillium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylphosphonium tetrakis(perfluorobiphenyl)borate,-   triethylsilylium tetrakis(perfluorobiphenyl)borate,-   benzene(diazonium) tetrakis(perfluorobiphenyl)borate,-   [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B],-   trimethylammonium tetraphenylborate,-   triethylammonium tetraphenylborate,-   tripropylammonium tetraphenylborate,-   tri(n-butyl)ammonium tetraphenylborate,-   tri(t-butyl)ammonium tetraphenylborate,-   N,N-dimethylanilinium tetraphenylborate,-   N,N-diethylanilinium tetraphenylborate,-   N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,-   tropillium tetraphenylborate,-   triphenylcarbenium tetraphenylborate,-   triphenylphosphonium tetraphenylborate,-   triethylsilylium tetraphenylborate,-   benzene(diazonium)tetraphenylborate,-   trimethylammonium tetrakis(pentafluorophenyl)borate,-   triethylammonium tetrakis(pentafluorophenyl)borate,-   tripropylammonium tetrakis(pentafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)    tetrakis(pentafluorophenyl)borate,-   tropillium tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis(pentafluorophenyl)borate,-   triphenylphosphonium tetrakis(pentafluorophenyl)borate,-   triethylsilylium tetrakis(pentafluorophenyl)borate,-   benzene(diazonium) tetrakis(pentafluorophenyl)borate,-   trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,-   triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,-   dimethyl(t-butyl)ammonium    tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)    tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   benzene(diazonium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tri(t-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dimethylanilinium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   benzene(diazonium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,-   dicyclohexylammonium tetrakis(pentafluorophenyl)borate,-   tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,-   tri(2,6-dimethylphenyl)phosphonium    tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis(perfluorophenyl)borate,-   1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,-   tetrakis(pentafluorophenyl)borate,-   4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, and-   triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).    13. The process of paragraph 11 or 12, wherein the process occurs at    a temperature of from about 0° C. to about 300° C., at a pressure in    the range of from about 0.35 MPa to about 10 MPa, and at a time up    to 300 minutes.    14. The process of paragraph 11, 12 or 13, further comprising    recovering (such as by solid liquid or vapor separation) polymer.    15. The process of any of paragraphs 11 to 14, wherein the olefins    comprise ethylene and or propylene.

EXPERIMENTAL

Abbreviations used herein include:

RT is room temperature, and is 23° C. unless otherwise indicated.

MAO is methyl alumoxane (30 wt % in toluene) obtained from Albemarle.

Catalyst Compounds:

Catalyst A: M is Ti, z is 2. Catalyst B: M is Hf, z is 2. Catalyst C÷Mis Ti, z is 0.Test Methods

Crystallization temperature (T_(c)) and melting temperature (or meltingpoint, T_(m)) are measured using Differential Scanning Calorimetry (DSC)on a commercially available instrument (e.g., TA Instruments 2920 DSC).Typically, 6 to 10 mg of molded polymer or plasticized polymer aresealed in an aluminum pan and loaded into the instrument at roomtemperature. Melting data (first heat) is acquired by heating the sampleto at least 30° C. above its melting temperature, typically 220° C. forpolypropylene, at a heating rate of 10° C./min. The sample is held forat least 5 minutes at this temperature to destroy its thermal history.Crystallization data are acquired by cooling the sample from the melt toat least 50° C. below the crystallization temperature, typically −50° C.for polypropylene, at a cooling rate of 20° C./min. The sample is heldat this temperature for at least 5 minutes, and finally heated at 10°C./min to acquire additional melting data (second heat). The endothermicmelting transition (first and second heat) and exothermiccrystallization transition are analyzed according to standardprocedures. The melting temperatures reported are the peak meltingtemperatures from the second heat unless otherwise specified.

For polymers displaying multiple peaks, the melting temperature isdefined to be the peak melting temperature from the melting traceassociated with the largest endothermic calorimetric response (asopposed to the peak occurring at the highest temperature). Likewise, thecrystallization temperature is defined to be the peak crystallizationtemperature from the crystallization trace associated with the largestexothermic calorimetric response (as opposed to the peak occurring atthe highest temperature).

Areas under the DSC curve are used to determine the heat of transition(heat of fusion, Hf, upon melting or heat of crystallization, H_(c),upon crystallization), which can be used to calculate the degree ofcrystallinity (also called the percent crystallinity). The percentcrystallinity (X %) is calculated using the formula: [area under thecurve (in J/g)/H° (in J/g)]*100, where H° is the ideal heat of fusionfor a perfect crystal of the homopolymer of the major monomer component.These values for H° are to be obtained from the Polymer Handbook, FourthEdition, published by John Wiley and Sons, New York, 1999, except that avalue of 290 J/g is used for H° (polyethylene), a value of 140 J/g isused for H° (polybutene), and a value of 207 J/g is used for H°(polypropylene).

Example 1: Reactor Screening of Catalyst A with MAO 30 wt %

In a dry box under nitrogen, 4 mg of Catalyst A was stirred with 0.5 mlMAO 30 wt % and 3 ml of dried toluene for 20 minutes at roomtemperature. 3.5 ml of the solution was syringed into a catalystcharger. The charger was removed from the box along with a syringe of0.3 ml TIBAL 1 M in hexanes. The catalyst charger was attached to a 1liter Zipper Autoclave reactor (prepared by nitrogen purge 1 hour at100° C. and then cooled to 25° C.). 0.3 ml of TIBAL was syringed intothe reactor. 600 mls of hexanes were added to the reactor and thestirrer set at 800 rpm. The temperature was increased to 80° C. Ethylenewas introduced to the reactor through a flowmeter at 200 psi. Oncetemperature and flow had settled, the catalyst was introduced to thereactor with high pressure nitrogen at 20 psi above the set pressure ofthe reactor (250 psi). The ethylene supply was maintained throughout thepolymerization through control by a flowmeter. After 45 minutes thereaction was stopped and cooled to room temperature. The pressure wasvented, and the reactor opened. 3 g of Polyethylene was recovered whichhad a peak melting point of 136.9° C.

Example 2: Reactor Screening of Catalyst B with MAO 30 wt %

The procedure of Example 1 was followed except that the reactor wasallowed to run for 60 minutes. After 60 minutes the reaction was stoppedand cooled to room temperature.

The pressure was vented, and the reactor opened. Zero grams ofPolyethylene was recovered.

Example 3: Reactor Screening of Catalyst C with MAO 30 wt %

The procedure of Example 1 was followed except that a solution of 30 mgof Catalyst C was stirred with 5 ml MAO 30 wt % and 5 ml of driedtoluene. 1 ml of this solution was syringed into the catalyst charger (3mg of catalyst), and transferred under Nitrogen into the reactor. After30 minutes the reaction was stopped and cooled to room temperature. Thepressure was vented, and the reactor opened. The reaction was repeated.1.8 g from Run #1 and 2.8 g (Run #2) of polyethylene were recovered. Thepolyethylene from Run #1 had a peak melting point of 132.2° C. Thepolyethylene from Run #2 had a peak melting point of 135.9° C.

Synthesis of Catalyst A Synthesis of TiCl₄.2THF

Anhydrous THF (tetrahydrofuran) (17.4 g, 240 mmol) was slowly added to asolution of titanium(IV) chloride (19.0 g, 100 mmol) in hexane under anitrogen (N₂) atmosphere. The temperature was maintained below 50° C.The solution was stirred for an additional 30 min after the THFaddition. The product was collected by filtration as yellow solid (32g).

Synthesis of (E)-2,2′-(ethene-1,2-diyl)diphenol (C₁₄H₁₂O₂)

Zn powder (15 g, 225 mmol was slowly added) to a solution of TiCl₄.2THF(37 g, 113 mmol) complex in THF. The solution was refluxed for 1.5 hourswith vigorous stirring. Salicylaldehyde (9.0 g, 75 mmol) was added andthe reaction mixture was refluxed for an additional 3.5 hours. Thesolution was cooled to room temperature and volatiles were removed undervacuum. The reaction was quenched with 2M hydrochloric acid (HCl) andwas extracted with ethyl acetate (EtOAc). The organic layer wasseparated and was stirred with aqueous potassium carbonate (K₂CO₃) for 2hours. A white solid precipitated in the aqueous phase. The crudereaction was filtered through Celite and the organic layer was separatedand dried with magnesium sulfate (MgSO₄). Volatiles were removed undervacuo. The crude product was washed with a minimum amount of chloroformfor 20 min. The product was collected by filtration as off-white solid(5.0 g).

¹H NMR (400 MHz, THF-d8) δ ppm; 8.38 (s, 2H); 7.56 (dd, 2H); 7.47 (s,2H); 7.04-6.98 (m, 2H); 6.78 (td, 2H); 6.74 (dd, 2H).

Synthesis of 2,2′-(ethane-1,2-diyl)diphenol (C₁₄H₁₄O₂)

Pd/C (1.2 g, 10%) was added to a solution of(E)-2,2′-(ethene-1,2-diyl)diphenol (9.5 g, 45 mmol) in THF in a FisherPorter Vessel with a Teflon coated magnetic stir bar and side arm withballoon attached for introduction of H₂ (hydrogen gas). The reactionflask was evacuated at room temperature and then charged with H₂. Theevacuation/H₂ exchange was performed three times overall. The reactionwas then stirred under H₂ atm for 16 hours. The reaction was filteredthrough celite and the solvent was removed in vacuo. White solid wascollected as pure product (8.0 g).

¹H NMR (400 MHz, THF-d8) δ ppm; 8.09 (s, 2H); 7.03 (dd, 2H); 6.97-6.92(m, 2H); 6.71-6.65 (m, 4H); 2.84 (s, 4H).

Synthesis of 1,2-bis(2-(methoxymethoxy)phenyl)ethane (C₁₈H₂₂O₄)

To a solution of 2,2′-(ethane-1,2-diyl)diphenol (7.0 g, 30 mmol) wasslowly added potassium hydride (KH) (2.64 g, 66 mmol). The reaction wasstirred for 10 min and then chloromethyl methyl ether (MOMCl) was added(5.8 g, 72 mmol). The reaction was stirred for additional 1.5 hr. TheTHF was removed in vacuo and the crude product was redissolved intodiethyl ether. Solids were removed by filtration on celite and thefiltrate was condensed in vacuum. The product was purified by flashchromatography on SiO₂ (200-400 mesh). The solvent mixture used forchromatography started with 74/25/1 (v/v/v) hexane/dichloromethane/EtOAcand increased in polarity to 48/50/2 (v/v/v)hexane/dichloromethane/EtOAc to elute the product band. After removal ofvolatiles the product was isolated as colorless oil (5.1 g).

¹H NMR (400 MHz, C₆D₆) δ ppm; 7.13-7.01 (m, 6H); 6.84 (td, 2H); 4.85 (s,4H); 3.14 (s, 6H); 3.13 (s, 4H).

Synthesis of C₁₈H₂₀Li₂O₄.Et₂O

To a solution of C₁₈H₂₂O₄ (5.1 g, 16.9 mmol) in diethyl ether was added10M n-butyl lithium (nBuLi) (4 ml, 39 mmol). The reaction was thenstirred for 3 hrs. The dilithio salt product was isolated by filtrationand washed by diethyl ether. 6.0 g of white solid was collected.

¹H NMR (400 MHz, DMSO-d6) δ ppm; 7.13-7.08 (m, 4H); 6.86 (t, 2H); 5.17(s, 4H); 3.36 (s, 6H); 2.81 (s, 4H).

Synthesis of 1,2-bis(2′-methoxy-2-(methoxymethoxy)biphenyl-3-yl)ethane

To a solution of C₁₈H₂₀Li₂O₄.Et₂O (2.80 g, 6 mmol) in THF (60 ml) wasadded Zinc dichloride (ZnCl₂) (1.66 g, 12 mmol). The mixture was stirreduntil all solids were dissolved. Pd(PtBu₃)₂ (120 mg) and1-iodo-2-methoxybenzene (3.0 g, 12.8 mmol) were then added and solutionwas stirred for 4 hrs at 60° C. The solvent was completely removed invacuo. The mixture was re-slurried into dichloromethane and was filteredon celite. The filtrate was dried in vacuo. The crude product waspurified by flash chromatography. The product collected via flashchromatography was then washed with hexane. 2.0 g of pure product wascollected as white solid.

¹H NMR (400 MHz, CDCl₃) δ ppm; 7.38-7.28 (m, 6H); 7.19-7.11 (m, 4H);7.02 (qd, 4H); 4.63 (s, 4H); 3.81 (s, 6H); 3.18 (s, 6H); 3.13 (s, 4H).

Synthesis of 3,3′-(ethane-1,2-diyl)bis(2′-methoxybiphenyl-2-ol)

C₃₂H₃₄O₆ (2 g) in ethanol was reflux for 2 hrs. Ethanol was removedunder vacuum and the mixture was reslurried into diethyl ether. 1.46 gof product was collected by filtration as a white solid.

¹H NMR (400 MHz, THF-d8) δ ppm; 7.32-7.23 (m, 4H); 7.10-6.95 (m, 8H);6.94 (s, 2H); 6.76 (t, 2H); 3.78 (s, 6H); 2.96 (s, 4H).

Synthesis of C₃₂H₃₆N₂O₄Ti

The above compound (85.3 mg, 0.2 mmol) andtetrakis(dimethylamino)titanium (Ti(NMe₂)₄) (44.8 mg, 0.2 mmol) weremixed in diethyl ether and stirred for 30 min. A yellow solidprecipitated from solution. The product was collected after solventremoval. ¹H NMR (400 MHz, CD₂Cl₂) δ ppm; 7.33-7.25 (m, 4H); 7.20 (dd,2H); 7.14-7.04 (m, 4H); 7.01-6.94 (m, 2H); 6.86 (t, 2H); 3.73 (s, 6H);2.75 (s, 12H); 2.74 (s, 4H).

Synthesis of Catalyst B C₃₂H₃₆N₂O₄Hf

C₂₈H₂₆O₄ (128 mg, 0.3 mmol) and tetrakis(dimethylamino)hafnium(Hf(NMe₂)₄) (107 mg, 0.3 mmol) were combined in diethyl ether andstirred for 30 min. After solvent removal, the product was collected asa white solid. 1H NMR (400 MHz, CD₂Cl₂) δ ppm; 7.29-6.59 (m, 14H); 3.71(s, 6H); 2.91 (s, 12H); 2.60 (s, 4H).

Synthesis of Catalyst C

2,2-Biphenylphenol (6.2 g) and dihydropyran (9.8 g) were dissolved inCH₂Cl₂ (60 ml) at RT. para-Toluenesulfonic acid (60 mg) was added andthe reaction was stirred for 1 minute at which time KOtBu (300 mg) wasadded at once. The volatiles were removed in vacuo and the crudepurified by filtration through SiO2 (50 g, 200-400 mesh) with 25/75 vvacetone/hexane solvent mixture (200 ml). The volatiles were removed andthe clear liquid product was dissolved in THF (50 ml) and deprotonatedwith nBuLi (5.5 g, 10 M). The yield was 6.0 g. All 6.0 g was slurried inTHF (60 ml). To the reaction mixture was added ZnCl₂ (3.4 g),2-iodoanisole (5.3 g) and Pd (P(tBu)₃)₂ (130 mg). The reaction mixturewas heated to 75° C. for 1 hr. The reaction was cooled to RT and thecrude reaction mixture washed with H₂O (2×50 ml) and extracted with Et₂O(100 ml). The volatiles were removed and the crude dissolved in acetone(60 ml). The product was collected as a white solid (1.3 g). TheTHP-group was removed by stirring the white solid in Et₂O (40 ml) andaqueous HCL (40 ml, 35 wt %) for 12 hr. The Et₂O layer was separated,aqueous layer extracted with 50 ml Et₂O, the Et₂O layers combined, driedwith MgSO₄ and volatiles removed. The crude product was purified bycolumn chromatography with SiO₂ (200-400 mesh) using 50/50 vvhexane/acetone to elute the ligand as a white solid (0.75 g).

¹H NMR (400 MHz, CD₂Cl₂) 7.42-7.35 (m, 6H), 7.30 (dd, 2H), 7.18-7.08 (m,6H), 6.55 (s, 2H), 3.87 (s, 6H).

The ligand (0.19 g) and Ti(NMe2)4 (0.107 g) were stirred together inCH2Cl2 (30 ml) at RT for 1 hr. A bright orange solid was collected,dried in vacuo and used without further purification (0.23 g).

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including.” Likewise, whenever a composition,an element or a group of elements is preceded with the transitionalphrase “comprising,” it is understood that we also contemplate the samecomposition or group of elements with transitional phrases “consistingessentially of,” “consisting of,” “selected from the group of consistingof,” or “is” preceding the recitation of the composition, element, orelements and vice versa.

What is claimed is:
 1. A catalyst compound represented by the formula:

wherein: a dotted line indicates a dative bond; M is a group 4 metal; zis 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, provided that when z is0, then there is a direct bond between the phenyl rings in place of the(CH₂)z group; each of R¹, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵ and R¹⁶ is, independently, hydrogen, a substituted C₁ to C₄₀hydrocarbyl group, a C₁ to C₄₀ unsubstituted hydrocarbyl group, or aheteroatom, provided that any of adjacent R groups may form a fused ringor multicenter fused ring system where the rings may be aromatic,partially saturated or saturated, and provided that R⁹ and R¹⁰ may notform a bridge; each of R² and R³, is, independently, hydrogen, asubstituted C₁ to C₄₀ hydrocarbyl group, a C₁ to C₄₀ unsubstitutedhydrocarbyl group, or a heteroatom, provided that R² and R³ may not forma bridge; and each X is, independently, a substituted C₁ to C₄₀hydrocarbyl group, a C₁ to C₄₀ unsubstituted hydrocarbyl group, ahydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, anamine, a phosphines, an ethers, a combination thereof, where two X'soptionally form a part of a fused ring or a ring system.
 2. The compoundof claim 1, wherein each of R² and R³, is, independently, hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, docecyl, t-butyl, isopropyl, phenyl, naphthyl or anisomer thereof.
 3. The compound of claim 1, wherein each X isindependently selected from Cl, Br, F, I, methyl, ethyl, propyl, butyl,pentyl, benzyl or an isomer thereof, and dimethylamido.
 4. The compoundof claim 1, wherein M is Ti and each of R¹, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ is, independently, hydrogen or t-butyl.5. A catalyst system comprising activator and the catalyst compound ofclaim
 1. 6. The catalyst system of claim 5, further comprising chaintransfer agent represented by the formula AlR₃, ZnR₂ where each R is,independently, a C₁-C₈ aliphatic radical.
 7. The catalyst system ofclaim 5, wherein the activator comprises alumoxane.
 8. The catalystsystem of claim 5, wherein the activator comprises a non coordinatinganion.
 9. The catalyst system of claim 5, wherein the catalyst systemcomprises a support.
 10. A process to polymerize olefins comprisingcontacting one or more olefins with the catalyst system of claim
 5. 11.The process of claim 10, wherein each X is, independently, selected fromthe group consisting of hydrocarbyl radicals having from 1 to 20 carbonatoms, hydrides, amides, alkoxides, sulfides, phosphides, halides,dienes, amines, phosphines, ethers, and a combination thereof, where twoX's optionally form a part of a fused ring or a ring system.
 12. Theprocess of claim 10, wherein M is Hf, Ti and/or Zr.
 13. The process ofclaim 10, wherein z is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or
 12. 14. Theprocess of claim 10, wherein z is
 0. 15. The process of claim 10,wherein z is
 1. 16. The process of claim 10, wherein the catalystcompound comprises one or more catalyst compounds represented by theformula:

wherein Me is methyl, Et is ethyl, Bz is benzyl, Ph is phenyl, tBu ist-butyl, and a dotted line indicates a dative bond.
 17. The process ofclaim 10, wherein the activator comprises alumoxane.
 18. The process ofclaim 17, wherein alumoxane is present at a molar ratio of aluminum tocatalyst compound transition metal of 100:1 or more.
 19. The process ofclaim 10, wherein the activator comprises a non-coordinating anionactivator.
 20. The process of claim 10, wherein the activator isrepresented by the formula:Z_(d) ⁺(A^(d−)) wherein Z is (L-H) or a reducible Lewis Acid, L is anneutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) isa non-coordinating anion having the charge d−; and d is an integer from1 to
 3. 21. The process of claim 10, wherein the activator isrepresented by the formula:Z_(d) ⁺(A^(d−)) wherein A^(d−) is a non-coordinating anion having thecharge d−; d is an integer from 1 to 3, and Z is a reducible Lewis acidrepresented by the formula: (Ar₃C⁺), where Ar is aryl or arylsubstituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl, or a substitutedC₁ to C₄₀ hydrocarbyl.
 22. The process of claim 10, wherein theactivator is one or more of: N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B],trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate,tripropylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, tri(t-butyl)ammonium tetraphenylborate,N,N-dimethylanilinium tetraphenylborate, N,N-diethylaniliniumtetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropillium tetraphenylborate, triphenylcarbeniumtetraphenylborate, triphenylphosphonium tetraphenylborate,triethylsilylium tetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate,1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, andtriphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). 23.The process of claim 10, wherein the process occurs at a temperature offrom about 0° C. to about 300° C., at a pressure in the range of fromabout 0.35 MPa to about 10 MPa, and at a time up to 300 minutes.
 24. Theprocess of claim 10, further comprising recovering polymer.
 25. Theprocess of claim 10, wherein the olefins comprise ethylene and/orpropylene.
 26. The process of claim 22, wherein the catalyst compoundcomprises one or more catalyst compounds represented by the formula:

wherein Me is methyl, t is ethyl, Bz is benzyl, Ph is phenyl, tBu ist-butyl, and a dotted line indicates a dative bond.
 27. The process ofclaim 16, wherein the activator is an alumoxane.
 28. The process ofclaim 26, wherein the catalyst system further comprising chain transferagent represented by the formula AlR₃, ZnR₂—where each R is,independently, a C₁-C₈ aliphatic radical.
 29. The process of claim 27,wherein the catalyst system further comprising chain transfer agentrepresented by the formula AlR₃, ZnR₂—where each R is, independently, aC₁-C₈ aliphatic radical.
 30. The catalyst system of claim 6, whereineach R is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, an isomerthereof or a combination thereof.
 31. The catalyst system of claim 28,wherein each R is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, anisomer thereof or a combination thereof.
 32. The catalyst system ofclaim 29, wherein each R is methyl, ethyl, propyl, butyl, pentyl, hexyl,octyl, an isomer thereof or a combination thereof.